Sulfonimide salts for battery applications

ABSTRACT

A class of sulfonimide salts for solid-state electrolytes can be synthesized based on successive S N Ar reactions of fluorinated phenyl sulfonimides: Fluorinated Aryl Sulfonimide Tags (FAST). The chemical and electrochemical oxidative stability of these FAST salts as well as other properties like solubility, Lewis basicity, and conductivity can be tuned by introducing different numbers and types of nucleophilic functional groups to the FAST salt scaffold.

CLAIM OF PRIORITY

This application claims the benefit of U.S. Provisional Application No.62/448,593 filed on Jan. 20, 2017, and U.S. Provisional Application No.62/519,683 filed on Jun. 14, 2017, each of which is incorporated byreference in its entirety.

TECHNICAL FIELD

This invention relates to materials for energy storage devices.

BACKGROUND

The increasing demands of modern electronics necessitate the developmentof energy storage devices that feature greater power and energydensities without compromising affordability and safety. With theadvantages of broad electrochemical stability window, high thermalstability, and low vulnerability towards moisture hydrolysis, lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI) is widely used as a lithiumsource in new battery chemistries with higher theoretical energydensities beyond lithium-ion battery, such as lithium-air andlithium-sulfur batteries. Moreover, LiTFSI is also the most studiedlithium salt especially in solid-state polymer electrolytes, due to itsdesirable solubility and excellent stability. However, chemically inertLiTFSI cannot be easily modified to optimize its properties or forconjugation to other molecules, polymers, or substrates to preparesingle-ion conducting polymer electrolytes.

SUMMARY

In one aspect, a composition can include:

wherein R₁ is —CF₃ or a fluorinated phenyl and R₂ is a fluorinatedphenyl or R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by anucleophile.

In certain circumstances, R₁ can be —CF₃.

In certain circumstances, R₁ can be a fluorinated phenyl. Thefluorinated phenyl can have at least two fluorine groups. For example,the fluorinated phenyl can have a formula

wherein each of X₁, X₂, X₃, X₄, and X₅, independently, is F or CF₃.

In another example, the fluorinated phenyl can have a formula

In certain circumstances, R₃ can be —CF₃ or a fluorinated phenyl and R₄can be a fluorinated phenyl, wherein at least one of R₃ and R₄ issubstituted by a nucleophile.

In certain circumstances, the fluorinated phenyl can have a formula

wherein each of X₁, X₂, X₃, X₄, and X₅, independently, is F, OR_(a), orNR_(c)R_(d), wherein R_(a) is C1-C6 alkyl, benzalkyl, or substituted orunsubstituted phenyl, R_(b) is C1-C6 alkyl, benzalkyl, or phenyl, R_(c)is C1-C6 alkyl, benzalkyl, or phenyl, or R_(b) and R_(c) together form athree to eight membered ring.

In certain circumstances, the fluorinated phenyl can have a formula

For example, each of X₁, X₃, and X₅, independently, can be methoxy,ethoxy, propoxy, butoxy, pentoxy, phenoxy, piperidinyl, orcycloocteneamino.

In certain circumstances, the compound can have formula (I) or formula(II)

P-Pip_(x)OR_(y)F_(z)  (I)

P-Pip_(x)OPh_(w)F_(z)  (II)

wherein P is a perfluoroarylsulfonimide anion, Pip is a piperidine, ORis an alkoxide, F is a fluorine substituent, OPh is phenoxide, and eachof x, y, z and w, independently, is 0, 1, 2 or 3, wherein the sum of x,y, and z or x, z and w is 0, 1, 2 or 3.

In certain circumstances OR is methoxy, ethoxy, isopropoxy orneopentoxy.

In another aspect, an energy storage device comprising an electrolyteincluding the composition including:

wherein R₁ is —CF₃ or a fluorinated phenyl and R₂ is a fluorinatedphenyl or R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by anucleophile.

In another aspect, a method of making a sulfonamide comprising combininga sulfonamide and a sulfonyl chloride according to equation (1)

to form a first sulfonamide, wherein R₁ is —CF₃ or a fluorinated phenyland R₂ is a fluorinated phenyl. In certain circumstances, the method caninclude exposing the first sulfonamide to a nucleophile according toequation (2)

wherein R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by thenucleophile.

Other aspects, embodiments, and features will be apparent from thefollowing description, the drawings, and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows synthesis of perfluoroarylsulfonimide anions A, B, and Cand their subsequent functionalization via S_(N)Ar reactions to generateFAST anions of the general formula P-Pip_(x)OR_(y)F_(z).

FIG. 2 shows chemical structures of FAST anions synthesized in this workvia S_(N)Ar reactions between various nucleophiles and parent salts A,B, or C.

FIGS. 3A-3C show crystal structures of FAST-Na salts A-PipOPh₂F₂(FIG.3A), A-PipOMe₂F₂(FIG. 3B) and A-PipOEt₂F₂(FIG. 3C). Atom color code:grey—carbon, white—hydrogen, red—oxygen, green—fluorine, yellow—sulfur,purple—nitrogen, and magenta—sodium.

FIG. 4 shows electrochemical oxidative potentials of select FAST saltscomputed using B3LYP/6-311++G(d,p) with geometries fully optimized atthe B3YLP/6-31G(d,p) level of theory in implicit DMSO solvent areplotted against the arithmetic average of the NPA partial charges ofaromatic carbons obtained at the optimized geometries.

FIG. 5 shows computed LUMOs (top row) and HOMOs (bottom row) of fourrepresentative FAST anions.

FIGS. 6A-6F show the influence of S_(N)Ar substitutions on theelectrochemical oxidative stability of representative FAST salts inpotentiostatic tests. FIG. 6A shows the current response ofA-OR_(y)F_(z) as functions of time show very low current up to 4.5 Vi.FIG. 6B shows the current response of different types of alkoxidesubstitutions in A-OR₃F₂ compared. FIG. 6C shows the cumulative chargeand estimated oxidized percentage of A-OR_(y)F_(z) and A-OR₃F₂calculated. FIGS. 6D and 6E respectively show the current response ofsalts with different numbers of piperidine type substitutions,A-Pip_(x)OR_(y)F_(z), and those in the A-PipOR₂F₂ series recorded. FIG.6F shows their cumulative charge and estimated oxidized percentage.

FIG. 7 shows chemical and electrochemical oxidative stability testresults for FAST salts. The black circles indicate the degradationpercentages of the sulfonimide salts after incubation with 10 equiv.Li₂O₂ and KO₂ in DMF for three days at 80° C.

FIG. 8A shows the measured chemical shift of ²³Na NMR signal forrepresentative FAST salts (the ²³Na signal from the inner standard,NaClO₄, is set to 0 ppm). FIG. 8B shows the ²³Na NMR chemical shift(relative to NaTFSI) and ion conductivity of 0.1 M 1,2-dimethoxyethanesolution at 25° C. versus the computed anion-Na⁺ association freeenergy, ΔG_(assoc), in implicit diethylether solvent with dielectricconstant set at 7.2 for representative FAST salts.

FIG. 9A shows the ion conductivities of solid state FAST-PEOelectrolytes prepared via blending representative LiFAST salts and PEO(molar ration of PEO repeat units and lithium ion [EO]:[Li⁺]=15:1) atvarious temperatures. FIG. 9B shows the conductivity of FAST-PEOelectrolytes at 60° C. versus computed free energy of anion-Li⁺association, ΔG_(assoc), in implicit diethylether solvent withdielectric constant set at 7.2.

FIG. 10 shows crystal structures of A-Pip₂F₃.H⁺.

FIG. 11 shows the computed Gibbs free energy for nucleophilicsubstitution by superoxide, ΔG_(nuc), at select carbon sites inA-OMe₃F₂, A-PipOMe₂F₂, and A-Pip₂OMeF₂ plotted against the increase inNPA partial charge of the attacking oxygen in superoxide (partial chargeof oxygen after the substitution reaction minus its charge before thereaction).

FIG. 12A shows ²³Na chemical shifts of representative B type and C typeFAST salts (the ²³Na signal from the inner standard, NaClO₄, is set to 0ppm). FIG. 12B shows the ²³Na NMR chemical shift (relative to NaTFSI)and ionic conductivities of 0.1 M 1,2-dimethoxyethane solution at 25° C.versus the computed free energy of anion-Na⁺ association, ΔG_(asso), forrepresentative B type and C type FAST salts in implicit diethylethersolvent with dielectric constant set at 7.2.

FIG. 13 shows NMR spectrum of A after ion exchange with lithiumchloride. The very strong ⁷Li peak and rather weak ²³Na peak indicatenearly complete replacement of Na⁺ by Li⁺.

FIG. 14 shows ¹H and ¹⁹F NMR of A-OPh₃F₂ before and after stability testin DMF. NMR solvent: d⁶-DMSO.

FIG. 15 shows ¹H and ¹⁹F NMR of A-OMe₃F₂ before and after stability testin DMF. NMR solvent: d⁶-DMSO.

FIG. 16 shows ¹H and ¹⁹F NMR of A-OEt₃F₂ before and after stability testin DMF. NMR solvent: d⁶-DMSO.

FIG. 17 shows ¹H and ¹⁹F NMR of A-OiPr₃F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 18 shows ¹H and ¹⁹F NMR of A-ONeop₃F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 19 shows ¹H and ¹⁹F NMR of A-PipOPh₂F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 20 shows ¹H and ¹⁹F NMR of A-PipOMe₂F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 21 shows ¹H and ¹⁹F NMR of A-PipOEt₂F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 22 shows ¹H and ¹⁹F NMR of A-PipOiPr₂F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 23 shows ¹H and ¹⁹F NMR of A-PipONeop₂F₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 24 shows ¹H and ¹⁹F NMR of A-Pip₂OMeF₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 25 shows ¹H and ¹⁹F NMR of A-Pip₂OEtF₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 26 shows ¹H and ¹⁹F NMR of A-Pip₂OiPrF₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 27 shows ¹H and ¹⁹F NMR of A-Pip₂ONeopF₂ before and after stabilitytest in DMF. NMR solvent: d⁶-DMSO.

FIG. 28 shows ¹H and ¹⁹F NMR of A-Pip₂F₃ before and after stability testin DMF. NMR solvent: d⁶-Acetone (before stability test) d⁶-DMSO (afterstability test).

FIG. 29 shows ¹H and ¹⁹F NMR of B-OEt₄ before and after stability testin DMF. NMR solvent: d⁶-Acetone (before stability test) d⁶-DMSO (afterstability test).

FIG. 30 shows ¹H and ¹⁹F NMR of B-OiPr₄ before and after stability testin DMF. NMR solvent: d⁶-Acetone (before stability test) d⁶-DMSO (afterstability test).

FIG. 31 shows ¹H and ¹⁹F NMR of A-NeopF₄. NMR solvent: d⁶-Acetone.

FIG. 32 shows ¹H and ¹⁹F NMR of A-Neop₂F₃. NMR solvent: d⁶-Acetone.

FIG. 33 shows ¹H and ¹⁹F NMR of A-PipF₄. NMR solvent: d⁶-Acetone.

FIG. 34 shows ¹H and ¹⁹F NMR of A-PipOiPrF₃. NMR solvent: d⁶-Acetone.

FIG. 35 shows ¹H and ¹⁹F NMR of A-PipOEtOiPrF₃. NMR solvent: d⁶-Acetone.

FIG. 36 shows ¹H and ¹⁹F NMR of A-o-PipONeopF₃. NMR solvent: d⁶-DMSO.

FIG. 37 shows ¹H and ¹⁹F NMR of A-o-PipONeop₂F₂.H⁺. NMR solvent:d⁶-Acetone.

FIG. 38 shows ¹H and ¹⁹F NMR of A-o-PipONeop₂F₂. NMR solvent:d⁶-Acetone.

FIG. 39 shows ¹H and ¹⁹F NMR of A-Pip₂F₃.H⁺. NMR solvent: CDCl₃.

FIG. 40 shows ¹⁹F NMR of B. NMR solvent: d⁶-Acetone.

FIG. 41 shows ¹⁹F NMR of C. NMR solvent: d⁶-Acetone.

FIG. 42 shows ¹H and ¹⁹F NMR of C-PipF₄. NMR solvent: d⁶-DMSO.

FIG. 43 shows ¹H and ¹⁹F NMR of C-PipOEt₂F₂. NMR solvent: d⁶-Acetone.

FIG. 44 shows ¹H and ¹⁹F NMR of C-PipOiPr₂F₂. NMR solvent: d⁶-Acetone.

FIG. 45 shows schematic illustration of an energy storage device.

DETAILED DESCRIPTION

Solid-state electrolytes are attracting great interest for theirapplications in potentially safe and stable high-capacity energy storagetechnologies. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) iswidely used as a lithium source, especially in solid-state polymerelectrolytes, due to its solubility and excellent chemical andelectrochemical stability. Unfortunately, chemically inert LiTFSI cannotbe easily modified to optimize its properties or allow for conjugationto other molecules, polymers, or substrates to prepare single-ionconducting polymer electrolytes. Chemical modifications of TFSI oftenerode its advantageous properties.

Disclosed herein is a class of modular TFSI analogs, Fluorinated ArylSulfonamide Tags (FAST), that are derived from successive nucleophilicaromatic substitution (S_(N)Ar) reactions of perfluoroarylsulfonimidesand the synthesis, chemical and electrochemical stability andconductivity study of FAST. The tunable chemical and oxidative stabilityas well as Lewis basicity of FAST salts opens up new opportunities forthe design and applications of polymer-FAST conjugates and single-ionconductors in solid-state electrolytes for safe and stable high-energystorage technologies.

Experimental studies and density functional theory calculations wereused to assess the electrochemical oxidative stability, chemicalstability, and degree of ion dissociation of FAST salts as a function oftheir structure. FAST salts offer a platform for accessing functionalsulfonimides without sacrificing the advantageous properties of TFSI.

The high energy density, reliability, and low cost of rechargeablelithium-ion batteries (LIBs) have revolutionized the consumer market forportable electronic devices. See J. M. Tarascon and M. Armand, Nature,2001, 414, 359-367, and S. Adv Mater Angewandte Chemie-InternationalEdition in English Chem Soc Rev Chu and A. Majumdar, Nature, 2012, 488,294-303, each of which is incorporated by reference in its entirety.However, the increasing demands of modern electronics necessitate thedevelopment of energy storage devices that feature greater power andenergy densities without compromising affordability and safety. See O.Schmidt, A. Hawkes, A. Gambhir and I. Staffell, Nat. Energy, 2017, 6,17110, A. Manthiram, X. Yu and S. Wang, Nat. Rev. Mater., 2017, 2,16103, and N. Nitta, F. Wu, J. T. Lee and G. Yushin, Mater. Today, 2015,18, 252-264, each of which is incorporated by reference in its entirety.As LIBs approach the theoretical specific energies of cathode/anodematerials, extensive studies have focused on finding new batterychemistries beyond LIBs. See D. Larcher and J. M. Tarascon, Nat. Chem.,2015, 7, 19-29, which is incorporated by reference in its entirety. Twotantalizing options are lithium-air (Li-air) batteries andlithium-sulfur (Li—S) batteries. See A. C. Luntz and B. D. McCloskey,Chem. Rev., 2014, 114, 11721-11750, Y.-C. Lu, B. M. Gallant, D. G.Kwabi, J. R. Harding, R. R. Mitchell, M. S. Whittingham and Y.Shao-Horn, Energy Environ. Sci., 2013, 6, 750-768, D. Aurbach, B. D.McCloskey, L. F. Nazar and P. G. Bruce, Nat. Energy, 2016, 1, 16128, Q.Pang, X. Liang, C. Y. Kwok and L. F. Nazar, Nat. Energy, 2016, 1, 16132,Y. X. Yin, S. Xin, Y. G. Guo and L. J. Wan, Angew. Chem. Int. Ed., 2013,52, 13186-13200, and A. Manthiram, S. H. Chung and C. Zu, Adv. Mater.,2015, 27, 1980-2006, each of which is incorporated by reference in itsentirety. While the gravimetric theoretical energy densities of thesebattery technologies are several times higher than conventional LIBs,both face numerous challenges that must be addressed beforecommercialization. See A. C. Luntz and B. D. McCloskey, Chem. Rev.,2014, 114, 11721-11750, Q. Pang, X. Liang, C. Y. Kwok and L. F. Nazar,Nat. Energy, 2016, 1, 16132, Y. X. Yin, S. Xin, Y. G. Guo and L. J. Wan,Angew. Chem. Int. Ed., 2013, 52, 13186-13200, A. Manthiram, S. H. Chungand C. Zu, Adv. Mater., 2015, 27, 1980-2006, J. Yi, S. Guo, P. He and H.Zhou, Energy Environ. Sci., 2017, 10, 860-884, S. Zhang, K. Ueno, K.Dokko and M. Watanabe, Adv. Energy Mater., 2015, 5, 1500117, and D. G.Kwabi, N. Ortiz-Vitoriano, S. A. Freunberger, Y. Chen, N. Imanishi, P.G. Bruce and Y. Shao-Horn, MRS Bull, 2014, 39, 443-452, each of which isincorporated by reference in its entirety. For example, new Li-air andLi—S batteries electrolytes with high conductivity (>10⁻⁴ S/cm at roomtemperature), stability, and safety are needed. See A. C. Luntz and B.D. McCloskey, Chem. Rev., 2014, 114, 11721-11750, J. Yi, S. Guo, P. Heand H. Zhou, Energy Environ. Sci., 2017, 10, 860-884, S. Zhang, K. Ueno,K. Dokko and M. Watanabe, Adv. Energy Mater., 2015, 5, 1500117, and K.Xu, Chem. Rev., 2014, 114, 11503-11618, each of which is incorporated byreference in its entirety. Most electrolyte materials that have beenstudied to date rely on mixtures of the salts lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI) or lithiumhexafluorophosphate (LiPF₆) and a suitable solvent and/or polymer. SeeK. Xu, Chem. Rev., 2014, 114, 11503-11618, and K. Xu, Chem. Rev., 2004,104, 4303-4418, each of which is incorporated by reference in itsentirety. Comparing LiTFSI and LiPF₆, LiTFSI offers a broadelectrochemical stability window, greater thermal stability, and higherresistance to hydrolysis, which lead it to be preferred in Li-air andLi—S batteries. See M. Ue, M. Takeda, M. Takehara and S. Mori, J.Electrochem. Soc., 1997, 144, 2684-2688, and R. Younesi, G. M. Veith, P.Johansson, K. Edstrom and T. Vegge, Energy Environ. Sci., 2015, 8,1905-1922, each of which is incorporated by reference in its entirety.Additionally, due to its high solubility in water (>21 M) and ability toform a passivation layer (mainly LiF), LiTFSI has been used in“water-in-salt” electrolytes enabling high-voltage aqueous lithium-ionbatteries. See L. Suo, F. Han, X. Fan, H. Liu, K. Xu and C. Wang, J.Mater. Chem. A, 2016, 4, 6639-6644, and L. Suo, O. Borodin, T. Gao, M.Olguin, J. Ho, X. Fan, C. Luo, C. Wang and K. Xu, Science, 2015, 350,938-943, each of which is incorporated by reference in its entirety.Moreover, encouraging results have been reported on utilizing TFSI saltsin sodium-air batteries and multivalent energy storage systems such asmagnesium batteries. See M. He, K. C. Lau, X. Ren, N. Xiao, W. D.McCulloch, L. A. Curtiss and Y. Wu, Angew. Chem. Int. Ed., 2016, 55,15310-15314, and X. Qu, Y. Zhang, N. N. Rajput, A. Jain, E. Maginn andK. A. Persson, J. Phys. Chem. C, 2017, 121, 16126-16136, each of whichis incorporated by reference in its entirety.

Though great progress has been made on the development of solid polymerelectrolytes wherein LiTFSI is dissolved in an aprotic polymer matrix ofpoly(ethylene oxide) (PEO), the transference number of Li⁺ in suchmaterials is typically as low as 0.2, which leads to polarization at thebattery electrodes and deleterious effects such as dendrite growth andlimited power delivery. See K. Timachova, H. Watanabe and N. P. Balsara,Macromolecules, 2015, 48, 7882-7888, R. Bouchet, S. Maria, R. Meziane,A. Aboulaich, L. Lienafa, J.-P. Bonnet, T. N. T. Phan, D. Bertin, D.Gigmes, D. Devaux, R. Denoyel and M. Armand, Nat. Mater., 2013, 12,452-457, E. Quartarone and P. Mustarelli, Chem. Soc. Rev., 2011, 40,2525-2540, Z. Xue, D. He and X. Xie, J. Mater. Chem. A, 2015, 3,19218-19253, W. H. Meyer, Adv. Mater., 1998, 10, 439-448, and A.Manthiram, X. Yu and S. Wang, Nat. Rev. Mater., 2017, 2, 16103, each ofwhich is incorporated by reference in its entirety. One strategy toimprove the Li⁺ (or Na⁺ in sodium batteries) transference numberinvolves anchoring the anions to a polymeric backbone, making the cationthe only mobile ion (i.e., single-ion conducting polymer electrolytes).See K. M. Diederichsen, E. J. McShane and B. D. McCloskey, ACS EnergyLett., 2017, 2, 2563-2575, which is incorporated by reference in itsentirety. Unfortunately, the TFSI anion is not readily chemicallymodifiable, and attempts to attach sulfonimides to polymers viareplacement of one or both of the electron withdrawing trifluoromethylgroups of TFSI with phenyl or alkyl groups often lead to materials withinferior properties compared to TFSI. See R. Bouchet, S. Maria, R.Meziane, A. Aboulaich, L. Lienafa, J.-P. Bonnet, T. N. T. Phan, D.Bertin, D. Gigmes, D. Devaux, R. Denoyel and M. Armand, Nat. Mater.,2013, 12, 452-457, H. T. Ho, A. Tintaru, M. Rollet, D. Gigmes and T. N.T. Phan, Polym. Chem., 2017, 8, 5660-5665, L. Porcarelli, A. S. Shaplov,F. Bella, J. R. Nair, D. Mecerreyes and C. Gerbaldi, ACS Energy Lett.,2016, 1, 678-682, Q. Ma, H. Zhang, C. Zhou, L. Zheng, P. Cheng, J. Nie,W. Feng, Y. S. Hu, H. Li, X. Huang, L. Chen, M. Armand and Z. Zhou,Angew. Chem. Int. Ed., 2016, 55, 2521-2525, and P. Murmann, P. Niehoff,R. Schmitz, S. Nowak, H. Gores, N. Ignatiev, P. Sartori, M. Winter andR. Schmitz, Electrochim. Acta, 2013, 114, 658-666, each of which isincorporated by reference in its entirety. Indeed, replacement of atrifluoromethyl group from TFSI with an electron rich group would beexpected to decrease the electrochemical oxidative stability of theresulting salt, increase Li⁺-anion association, and potentially reduceion conductivity. See S. Ladouceur, S. Paillet, A. Vijh, A. Guerfi, M.Dontigny and K. Zaghib, J. Power Sources, 2015, 293, 78-88, V. Morizur,S. Olivero, J. R. Desmurs, P. Knauth and E. Dunach, New J. Chem., 2014,38, 6193-6197, and V. Morizur, M. Braglia, S. Olivero, J.-R. Desmurs, P.Knauth and E. Dunach, New J. Chem., 2016, 40, 7840-7845, each of whichis incorporated by reference in its entirety.

In certain embodiments, TFSI derivatives where one or bothtrifluoromethyl groups can be replaced with functional yet stillelectron withdrawing substituents, such that the beneficial propertiesof TFSI are not compromised. Perfluoroarylsulfonimides A, B, and C(FIG. 1) can be starting points to achieve this goal. Note that thecations used in this study, Na⁺ and Li⁺, are not shown in FIG. 1. Theinstallation of perfluoroaryl substituents in these compounds canmaintain the electron deficient nature of the anion and open thepossibility of chemical modification via nucleophilic aromaticsubstitution (S_(N)Ar) reactions. Thereby a class of sulfonimides, whichis called “Fluorinated Aryl Sulfonimide Tags” (FAST), can besynthesized. Successive S_(N)Ar reactions between A, B, or C and oxygen-and/or nitrogen-base nucleophiles enabled rational tuning of theelectron density, electrochemical oxidative stability, chemicalstability toward superoxide and peroxide anions, and Lewis basicity ofFAST salts as assessed by both experimental studies and densityfunctional theory (DFT) calculations. This design led to several FASTsalts that display electrochemical oxidative stability at 4.0 V_(Li),negligible chemical degradation, and reasonable ion conductivity in1,2-dimethoxyethane (DME). FAST salts offer a synthetically tunableplatform for the identification of optimal anion structures that couldreplace TFSI in a variety of applications.

In general, a composition can include:

wherein R₁ is —CF₃ or a fluorinated phenyl and R₂ is a fluorinatedphenyl or R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by anucleophile.

In certain embodiments, R₁ can be —CF₃.

In other embodiments, R₁ can be a fluorinated phenyl.

In certain embodiments, the fluorinated phenyl can have at least twofluorine groups, for example, the fluorinated phenyl can have a formula

wherein each of X₁, X₂, X₃, X₄, and X₅, independently, is F or CF₃.

In other embodiments, the fluorinated phenyl can have a formula

In certain embodiments, the compound has the formula

wherein R₃ can be —CF₃ or a fluorinated phenyl and R₄ can be afluorinated phenyl, wherein at least one of R₃ and R₄ can be substitutedby a nucleophile.

The nucleophile can be an amine, alkoxy, aryloxy, alkylthio, alkyl orsimilar nucleophilic moiety. For example, the nucleophile can be —OR_(a)or —NR_(c)R_(d), wherein R_(a) is C1-C6 alkyl, benzalkyl, or substitutedor unsubstituted phenyl, R_(b) is C1-C6 alkyl, benzalkyl, or phenyl,R_(c) is C1-C6 alkyl, benzalkyl, or phenyl, or R_(b) and R_(c) togetherform a three to eight membered ring.

In other embodiments, the fluorinated phenyl can have a formula

wherein each of X₁, X₂, X₃, X₄, and X₅, independently, is F, OR_(a), orNR_(e)R_(d), wherein R_(a) is C1-C6 alkyl, benzalkyl, or substituted orunsubstituted phenyl, R_(b) is C1-C6 alkyl, benzalkyl, or phenyl, R_(c)is C1-C6 alkyl, benzalkyl, or phenyl, or R_(b) and R_(c) together form athree to eight membered ring.

In other embodiments, the fluorinated phenyl can have a formula

In certain examples, each of X₁, X₃, and X₅, independently, can bemethoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, piperidinyl, orcycloocteneamino.

The composition can be made by a number of methods. For example, amethod of making a sulfonamide can include combining a sulfonamide and asulfonyl chloride according to equation (1)

to form a first sulfonamide, wherein R₁ is —CF₃ or a fluorinated phenyland R₂ is a fluorinated phenyl.

The method can include exposing the first sulfonamide to a nucleophileaccording to equation (2)

wherein R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by thenucleophile.

In other aspects, an energy storage device can include an electrolyteincluding the composition disclosed herein.

An energy storage device can include a voltage source electricallyconnected to a first electrode and a second electrode; and anelectrolyte in contact with the first electrode and the secondelectrode; wherein the electrolyte includes a composition of formula (I)or formula (II):

P-Pip_(x)OR_(y)F_(z)  (I)

P-Pip_(x)OPh_(w)F_(z)  (II)

wherein P is a perfluoroarylsulfonimide anion, Pip is a piperidine, R isan alkoxide, F is a fluorine substituent, Ph is phenoxide, and x, y, zand w are the numbers of piperidine, alkoxide, fluorine and phenoxidesubstituents, respectively.

Where a system is described as involving a first electrode and/or asecond electrode (one or both of which can include a catalyticmaterial), with production of oxygen gas via water electrolysis at thefirst electrode and/or production of hydrogen gas at the secondelectrode, it is to be understood that the first electrode canfacilitate oxidation of water or another species to produce oxygen gasor another oxidized product. Examples of reactants that can be oxidizedin this context can include methanol, formic acid, ammonia, etc.Examples of oxidized products can include CO₂, N₂, etc. At the secondelectrode, a reaction can be facilitated in which water (or hydrogenions) is reduced to make hydrogen gas, but it is to be understood that avariety of reactants not limited to water (e.g., metal oxides or ions,acetic acid, phosphoric acid, etc.) can be reduced to form hydrogen gasand/or metals and/or other products of the reduction reaction (e.g.,metal hydroxides, acetate, phosphate, etc.). This reaction at the secondelectrode can be run in reverse, in “fuel cell” operation, such thathydrogen gas (and/or other exemplary products noted above) is oxidizedto form water (and/or other exemplary reactants noted above). In somecases, the compositions, electrodes, methods, and/or systems may be usedfor reducing hydrogen gas. In some cases, the compositions, electrodes,methods, and/or systems may be used in connection with aphotoelectrochemical cell.

Electrolytic devices, fuel cells, metal-ion batteries (e.g. lithium-ionbatteries) and metal-air batteries (e.g. lithium-air batteries) arenon-limiting examples of energy storage devices provided herein. Energycan be supplied to electrolytic devices by photovoltaic cells, windpower generators, or other energy sources.

An energy storage device may be combined with additional energy storagedevice to form a larger device or system. This may take the form of astack of devices or subsystems (e.g., fuel cell and/or electrolyticdevice and/or metal-air battery) to form a larger device or system.Various components of a device, such as the electrodes, power source,electrolyte, separator, container, circuitry, insulating material, gateelectrode, etc. can be fabricated by those of ordinary skill in the artfrom any of a variety of components, as well as those described in anyof those patent applications described herein. Components may be molded,machined, extruded, pressed, isopressed, infiltrated, coated, in greenor fired states, or formed by any other suitable technique. Those ofordinary skill in the art are readily aware of techniques for formingcomponents of devices herein.

Generally speaking, an energy storage device includes two electrodes(i.e., an anode and a cathode) in contact with an electrolyte. Theelectrodes are electrically connected to one another; the electricalconnection can, depending on the intended use of the system, include apower source (when the desired electrochemical reactions requireelectrical energy) or an electrical load (when the desiredelectrochemical reactions produce electrical energy). An energy storagedevice can be used for producing, storing, or converting chemical and/orelectrical energy.

FIG. 45 schematically illustrates energy storage device 1, whichincludes anode 2, cathode 3, electrolyte 4, anode collector 5, andcathode collector 6. The battery can include a housing including anelectrolyte (not shown). The battery can be a lithium battery, forexample, a lithium ion battery.

EXAMPLES

The perfluoroarylsulfonimide sodium salts A and C were prepared startingfrom pentafluorobenzene sulfonyl chloride in good yield (>82%), whereassalt B was prepared via condensation of4-trifluoromethyl-2,3,5,6-tetrafluorobenzenesulfonyl bromide (see V. E.Platonov, A. M. Roman A. Bredikhin and V. V. K. Maksimov, J. FluorineChem., 2010, 131, 13-16, which is incorporated by reference in itsentirety) and trifluoromethanesulfonamide in 72% yield. With thesecompounds in hand, the synthesis of a library of FAST salts (FIG. 2)were started via S_(N)Ar reactions between A, B, or C and a variety ofnucleophiles selected to assess the impact of steric bulk andelectronics on the properties of FAST salts: phenoxide (OPh), alkoxides(OR: OMe, OEt, OiPr, and ONeop), and piperidine (Pip). Throughout thiswork, the general notation P-Pip_(x)OR_(y)F_(z) represents each FASTsalt, where P is the parent salt (A, B, or C), and x, y, and z are thenumbers of piperidine, alkoxide, and fluorine substituents,respectively. All FAST sodium salts were characterized by ¹H, ¹³C, ¹⁹FNMR, MS, and in some cases, single crystal X-ray crystallography.

Differences in the reactivity of the various nucleophiles in this systemwere exploited to control the substituent patterns in the resulting FASTsalts. For example, selective S_(N)Ar of the para fluorine atom of Awith Pip could be achieved to provide A-PipF₄; subsequent S_(N)Ar of theremaining ortho fluorine atoms with OPh, OMe, or OEt groups providedA-PipOPh₂F₂, A-PipOMe₂F₂ and A-PipOEt₂F₂, respectively. The structuresof the sodium salts of these compounds were confirmed by X-raycrystallography (FIG. 3). Notably, though these newly introduced N and Osubstituents are electron donating, this substitution pattern maintainsthe two electron-withdrawing meta fluorine substituents (Hammettparameters for fluorine: σ_(meta)=0.34 versus σ_(para)=0.06). As seen inFIG. 3, the sulfonimides in these structures are present as their freebase; the sodium cations are not coordinated to the nitrogen but insteadcoordinate to the oxygen atoms from the sulfonimide groups, alkoxidegroups, and/or adventitious water (FIG. 3B). When two piperidine groupsare introduced onto the A scaffold the resulting FAST salts (e.g.,A-Pip₂F₃ and its derivatives A-Pip₂ORF₂) are much less acidic (they areprotonated during aqueous washing); the crystal structure of A-Pip₂F₃.H⁺(FIG. 10) reveals that the proton is coordinated by the nitrogen atom ofthe ortho-Pip. Therefore, FAST salts containing two Pip substituentswere deprotonated with sodium hydroxide prior to further investigations.

The electrochemical oxidative stability and average partial charge ofaromatic carbons, c., obtained using Natural Population Analysis (NPA)(see J. P. Foster and F. Weinhold, J. Am. Chem. Soc., 1980, 102,7211-7218, and A. E. Reed, R. B. Weinstock and F. Weinhold, J. Chem.Phys., 1985, 83, 735-746, each of which is incorporated by reference inits entirety) of select tri-substituted FAST salts as well as A,A-NeopF₄, and A-Neop₂F₃ depicted in FIG. 2 were evaluated using DFTcalculations (FIG. 4) following the BANE framework developed recently.See S. Feng, M. Chen, L. Giordano, M. Huang, W. Zhang, C. V. Amanchukwu,R. Anandakathir, Y. Shao-Horn and J. A. Johnson, J. Mater. Chem. A,2017, 5, 23987-23998, which is incorporated by reference in itsentirety. In FIG. 4, the electrochemical oxidation potentials inexperimentally measured scale versus Li/Li⁺, plotted on the right axis,were converted from the computed -G_(ox) in eV by the subtraction of 1.4V. See S. Trasatti, Pure Appl. Chem., 1986, 58, 955-966, and L. Xing, O.Borodin, G. D. Smith and W. Li, J. Phys. Chem. A, 2011, 115,13896-13905, each of which is incorporated by reference in its entirety.

Higher computed electrochemical oxidation potential correlated well withhigher average aromatic carbon charge, c₊. More specifically, FAST saltswith the greatest number of electron donating Pip groups (e.g.,A-Pip₂ORF₂) exhibit the lowest c₊ and electrochemical oxidativestability. FAST derivatives with one Pip group (e.g., A-PipOR₂F₂) showedhigher c₊ and electrochemical oxidative stability than A-Pip₂ORF₂. Asexpected, the trialkoxide derivatives A-OR₃F₂, in turn, exhibited higherc₊ and electrochemical oxidative stability than A-PipOR₂F₂. Finally, inthe order of A-Neop₂F₃, A-NeopF₄, and A, as the number of electronwithdrawing F atoms increases, the computed c. and electrochemicaloxidative stability increase almost linearly.

To further understand the electrochemical oxidative stability of theFAST salts, HOMO and LUMO maps for four representative salts,A-ONeop₃F₂, A-PipONeop₂F₂, A-o-PipONeop₂F₂, and A-Pip₂ONeopF₂ werecompared (FIG. 5). The HOMO/LUMO maps were generated using the optimizedgeometries obtained at B3LYP/6-31G(d,p). The HOMO/LUMO energy in eV wereobtained at B3LYP/6-311++G(d,p) level of theory with geometriesoptimized using B3LYP/6-31G(d,p). Atom color code: grey—carbon,white—hydrogen, red—oxygen, aqua—fluorine, yellow—sulfur, andblue—nitrogen.

These salts show similar LUMOs but significantly different HOMOs: theHOMO of A-ONeop₃F₂ is uniformly distributed on the aromatic ring withlittle density on the oxygen atoms of the alkoxide substituents. FASTsalts with a Pip group featured HOMOs that were heavily localized on thePip nitrogen atom. Surprisingly, the HOMO maps of A-PipONeop₂F₂ andA-o-PipONeop₂F₂ are drastically different. The HOMO of A-PipONeop₂F₂ isdistributed on both the benzene ring and the Pip nitrogen atom, whilenearly all the HOMO is concentrated on the Pip nitrogen atom in theortho position in both A-o-PipONeop₂F₂ and A-Pip₂ONeopF₂. Theseobservations may explain the observed basicity of A-o-PipONeop₂F₂ andA-Pip₂ONeopF₂ that was not observed for other salts.

Experimental measurements were carried out to evaluate theelectrochemical oxidative stability of several of these FAST salts underan oxygenated environment for comparison to the DFT computed trendsobtained in implicit DMSO solvent. The electrochemical oxidativestability of the FAST salts was determined using potentiostaticmeasurements in an electrochemical cell (glass fiber separatorimpregnated with 0.02 M sulfonimide dissolved in propylene carbonate(PC) solution sandwiched between Li metal foil and stainless steel meshcurrent collector), which was pressurized with oxygen and held atpotentials from 3.0 to 4.5 V_(Li) for 3 h each. PC was chosen as thesolvent due to its superior electrochemical stability (see K. Xu, Chem.Rev., 2004, 104, 4303-4418, and M. Ue, M. Takeda, M. Takehara and S.Mori, J. Electrochem. Soc., 1997, 144, 2684-2688, each of which isincorporated by reference in its entirety), although it should be notedthat its vulnerability against nucleophilic substitution makes itunsuitable as electrolyte solvent for Li—O₂ battery. See D. Aurbach, M.Daroux, P. Faguy and E. Yeager, J. Electroanal. Chem., 1991, 297,225-244, and S. A. Freunberger, Y. Chen, Z. Peng, J. M. Griffin, L. J.Hardwick, F. Barde, P. Novak and P. G. Bruce, J. Am. Chem. Soc., 2011,133, 8040-8047, each of which is incorporated by reference in itsentirety. A relatively low concentration, 0.02 M, was employed toaccommodate the low solubility of several FAST salts such as A-Pip₂OEt₂in PC. The current response, cumulative charge, and estimated percentageof salt oxidation at each potential step from 3.6 V_(Li) to 4.5 V_(Li)for select salts are shown in FIG. 6. Measurements were performed usingan electrochemical cell pressurized with oxygen and consisting of astainless steel mesh current collector, 90 μL 0.02 M FAST-PC solution,one glass fiber separator, and Li metal.

The percentage of electrochemically oxidized salt was calculated basedon the assumption that the oxidation of one FAST salt molecule producesone electron. Deviation from this assumption and the presence ofimpurities can lead to overestimation of the electrochemical oxidationpercentage, which can explain why several salts showed electrochemicaloxidation percentages that are close to or even greater than 100%. InFIGS. 6A and 6C, the series of A, A-ONeopF₄, A-ONeop₂F₃, A-ONeop₃F₂ arecompared. All four salts in this series, which feature 2 to 5 fluorineatoms and 0 to 3 ONeop substituents on the aromatic ring, were verystable towards oxidation with approximately 2% and 6% oxidized uponcharging to 4.2 V and 4.5 V_(Li), respectively (FIG. 6C). Upon chargingto 4.5 V, TFSI exhibited electrochemical oxidation roughly an order ofmagnitude lower than the four salts in this series. However, these fourssalts are more stable than (phenylsulfonyl)(trifluoromethyl)sulfonimide(Ph-TFSI), a widely used TFSI alternative in battery applications. SeeR. Bouchet, S. Maria, R. Meziane, A. Aboulaich, L. Lienafa, J.-P.Bonnet, T. N. T. Phan, D. Bertin, D. Gigmes, D. Devaux, R. Denoyel andM. Armand, Nat. Mater., 2013, 12, 452-457, and A. A. Rojas, K. Thakker,K. D. McEntush, S. Inceoglu, G. M. Stone and N. P. Balsara,Macromolecules, 2017, 50, 8765-8776, each of which is incorporated byreference in its entirety. Next, the influence of the substitutionpattern on the oxidative stability of triply substituted salts A-OR₃F₂was measured (FIGS. 6B and 6C). These salts showed excellent oxidativestability at voltages <4.0 V_(Li) with the exception of A-OMe₃F₂, whichexhibited significant oxidative current at 3.8 V_(Li). Generally, theFAST salts with bulkier alkoxide groups (e.g., OiPr and ONeop) exhibitedsuperior stability than those with smaller substituents such as OMe andOEt at high voltage (>4.0 V_(Li)). The influence of Pip on theelectrochemical stability was investigated by comparing A-ONeop₃F₂,A-PipONeop₂F₂, A-o-PipONeop₂F₂, and A-Pip₂ONeopF₂ (FIGS. 6D and 6F). Itis observed that while A-ONeop₃F₂ is very stable at 4.2 V_(Li) (˜2%electrochemical oxidation), A-Pip₂ONeopF₂ and A-o-PipONeop₂F₂experienced 11% and 21% oxidation upon charging to 4.2 V_(Li),respectively. This stability trend matches the DFT calculationspresented in FIG. 4(A-ONeop₃F₂>A-PipONeop₂F₂>A-o-PipONeop₂F₂≈A-Pip₂ONeopF₂). Finally,several A type FAST salts with one piperidine group A-PipOR₂F₂ and Btype FAST salts B—OR₄ were tested and compared in FIGS. 6E and 6F. Asshown by the cumulative charge and estimated oxidized percentage in FIG.6F, A-PipOR₂F₂ and B—OR₄ generally have higher charge accumulation andworse electrochemical oxidative stability than A-OR₃F₂ at >4.0 V_(Li).Overall, most of the salts in FIG. 3 show electrochemical oxidativestability at 4.0 V_(Li) and thus are promising candidates in diversebattery chemistries. Notably, A-ONeop₃F₂ was extremely stable toelectrochemical oxidation (up to 4.5 V_(Li) with oxidative current lessthan 0.25 μA and oxidation percentage is less than 6%).

Next, the chemical stability of various FAST salts was investigatedunder solution conditions designed to mimic the oxygen electrode of atypical aprotic Li-air battery. See S. Feng, M. Chen, L. Giordano, M.Huang, W. Zhang, C. V. Amanchukwu, R. Anandakathir, Y Shao-Horn and J.A. Johnson, J. Mater. Chem. A, 2017, 5, 23987-23998, J. R. Harding, C.V. Amanchukwu, P. T. Hammond and Y Shao-Horn, J. Phys. Chem. C, 2015,119, 6947-6955, and C. V. Amanchukwu, J. R. Harding, Y Shao-Horn and P.T. Hammond, Chem. Mater, 2015, 27, 550-561, each of which isincorporated by reference in its entirety. In FIG. 7, Percentdegradation was quantified by ¹H NMR using 4-methoxybiphenyl as areference standard. The electrochemical oxidation percentages of thecorresponding FAST salts in the potentiostatic tests at the end of the4.2-V step are shown by the blue circles.

Each FAST salt was dissolved in DMF (20 mg/mL) and mixed with 10equivalent Li₂O₂, KO₂, and 1 equivalent 4-methoxybiphenyl as internalstandard (for quantitative NMR analysis); the mixture was stirred at 80°C. for 3 days. The supernatant of the mixture was characterized by ¹H,¹⁹F-NMR, and liquid chromatography-mass spectrometry (LC-MS). Generally,FAST salts with a greater number of aryl fluoride groups displayed lowerchemical stability: for salts derived from A and C, only those with twometa fluorine atoms have negligible degradation, whereas in saltsderived from B no aryl fluorides were tolerated due to the strongelectron withdrawing effect of —CF₃ group (σ_(para)=0.54). Fortri-substituted salts derived from A (FIGS. 1 and 2), the chemicalstability was strongly affected by the identity and pattern of thesubstituents. FIG. 5 provides a comparison of the percentage ofdegradation (obtained by quantitative ¹H NMR) of each salt. For saltsderived from A, it was observed that bulkier —OR substituents improvedthe stability against chemical degradation. A-OMe₃F₂ was observed todegrade almost completely (91%) while no degradation was detected forA-ONeop₃F₂. FAST salts with Pip groups exhibited greater chemicalstability than those with —OR substitutions: the degraded percentagedecreased from 65% in A-OPh₃F₂ and 91% in A-OMe₃F₂ to 16% in A-PipOPh₂F₂and 15% in A-PipOMe₂F₂. When two Pip groups were introduced(A-Pip₂ORF₂), less than 4% degradation was observed regardless of theidentity of R. These experimental results for chemical stability areinversely correlated with the calculated average carbon atomic chargeson the aromatic ring: A-Pip₂ORF₂>A-PipOR₂F₂>A-OR₃F₂, which supports theexpectation that more electron rich FAST salts should be lesssusceptible to nucleophilic attack. Furthermore, the Gibbs free energywas computed for nucleophilic substitution by superoxide, ΔG_(nuc), atselect carbon sites (i.e., O—CH₃) in A-OMe₃F₂, A-PipOMe₂F₂, andA-Pip₂OMeF₂ (FIG. 11); the computed trend of ΔG_(nuc)(A-OMe₃F₂<A-PipOMe₂F₂<A-Pip₂OMeF₂) follows the trend in the chemicalstability of these salts determined experimentally. Finally, thecomputed ΔG_(nuc) was plotted against the increase in the NPA partialcharge of the attacking oxygen in superoxide (partial charge of theoxygen after the substitution reaction minus its partial charge beforethe reaction; FIG. 11). It is observed that a larger increase in theoxygen partial charge corresponds to a more favourable ΔG_(nuc) in thesesalts; this correlation was also observed in the recent study on thenucleophilic substitution of small organic molecules such as carbonatesand ethers by superoxide. See S. Feng, M. Chen, L. Giordano, M. Huang,W. Zhang, C. V. Amanchukwu, R. Anandakathir, Y. Shao-Horn and J. A.Johnson, J. Mater. Chem. A, 2017, 5, 23987-23998, which is incorporatedby reference in its entirety. This trend suggests that a larger increasein the attacking oxygen partial charge indicates strongerelectron-donating strength of superoxide at the carbon site, which givesrise to more favourable ΔG_(nuc).

The ion conductivity in liquid electrolyte depends upon two factors:charge carrier concentration and mobility. With the same concentrationof salts, the extent to which the salt is dissociated determines thecharge carrier concentration. Generally, salt anions with higher Lewisbasicity interact more strongly with alkali metal cations, and thusincrease the extent of anion-cation association. See S. S. Sekhon, N.Arora and H. P. Singh, Solid State Ion., 2003, 160, 301-307, C. M.Burke, V. Pande, A. Khetan, V. Viswanathan and B. D. McCloskey, Proc.Natl. Acad. Sci. U.S.A., 2015, 112, 9293-9298, and M. Schmeisser, P.Illner, R. Puchta, A. Zahl and R. van Eldik, Chemistry, 2012, 18,10969-10982, each of which is incorporated by reference in its entirety.The TFSI anion is well known for being an “innocent” anion with weakinteractions with metal ions. See M. Schmeisser, P. Illner, R. Puchta,A. Zahl and R. van Eldik, Chemistry, 2012, 18, 10969-10982, which isincorporated by reference in its entirety. To compare the FAST saltswith TFSI and evaluate the extent of ion dissociation, the anion-cationinteraction strengths for the FAST salts were determined by ²³Na NMR.See M. Schmeisser, P. Illner, R. Puchta, A. Zahl and R. van Eldik,Chemistry, 2012, 18, 10969-10982, and R. H. Erlich and A. I. Popov, J.Am. Chem. Soc., 1971, 93, 5620-5623, each of which is incorporated byreference in its entirety. The sodium salts were prepared as 0.1 Msolutions in nitromethane with 0.25 M NaClO₄ in DMSO as the internalstandard. The ²³Na chemical shifts of FAST salts relative to NaTFSI areshown in FIG. 8A. It is immediately obvious that the nature of the anionplays an important role in the resulting chemical shift. For example,A-OR₃F₂ and A-PipOR₂F₂ have ²³Na signals shift toward down field,indicating stronger anion-Na⁺ interaction than the parent type A and Bsalts. A considerable amount of line broadening was also observed andcan be attributed to the formation of more ion pairs. See R. H. Erlichand A. I. Popov, J. Am. Chem. Soc., 1971, 93, 5620-5623, which isincorporated by reference in its entirety. As the FAST salt anionsbecome more electron rich (i.e., as the number of F atoms decreases),they seem to become more Lewis basic, display stronger interactions withNa⁺ and produce more ion pairs. To validate this hypothesis and studythe effect of different substitution groups on anion-Na⁺ interaction andion conductivity, the calculated Gibbs free energy of ion pairassociation, ΔG_(assoc), versus the relative ²³Na chemical shifts aswell as the ion conductivities of 1,2-dimethoxyethane (DME) solutionscontaining several FAST salts at 0.1 M experimentally obtained at 25° C.was plotted (FIG. 8B). Implicit diethylether solvent with dielectricconstant set at 7.2 was used to mimic the solvent used for conductivitystudies (DME). As expected, salts with more negative calculatedΔG_(assoc) values (more favorable anion-Na⁺ association) have moredown-field shift in ²³Na NMR spectrum and displayed lower conductivity.More specifically, it was observed that solutions containing type A andB salts have ion conductivities that are a factor of 2 and 1.5,respectively, lower than that of NaTFSI while A-ONeop₃F₂, A-PipF₄ andA-PipONeop₂F₂ exhibit conductivities that are 4 to 7 times lower. Theconductivities of solutions containing these salts are inversely relatedto the salt anion Lewis basicity and anion-cation interaction strength.Furthermore, ²³Na NMR chemical shift of other B type and C type saltswere also measured shown in FIG. 12A. Here acetonitrile was chosen assolvent due to low solubility of B and C type salts in nitromethane.Acetonitrile solvates Na⁺ better than nitromethane and thus decreasesthe anion-Na⁺ interaction strength difference. See R. H. Erlich and A.I. Popov, J. Am. Chem. Soc., 1971, 93, 5620-5623, which is incorporatedby reference in its entirety. Nevertheless, it was observed that saltswith more S_(N)Ar substitutions have ²³Na signal shift toward down fieldand line broadening comparing with B and C parent salts (FIG. 12A);these salts also exhibit more favorable ΔG_(assoc) for anion-Na⁺association and lower ion conductivity in DME solution (FIG. 12B).Overall, salts with more S_(N)Ar substitutions among all three typeshave greater Lewis basicity, which leads to stronger interaction withNa⁺ and more negative ΔG_(assoc) values. These results highlight thebalance of factors that must be considered in the design of functionalTFSI derivatives.

The Li FAST salts could be readily acquired by ion exchange of the Nasalts. Four Li salts were prepared from A, A-PipF₄, A-ONeop₃F₂, andA-PipONeop₂F₂. The ⁷Li and ²³Na NMR spectra show nearly completereplacement of Na⁺ by Li⁺ in A (FIG. 13). The ionic conductivities ofsolid-state polymer electrolytes prepared by blending these Li saltswith PEO (10 kDa; molar ratio of PEO repeat unit and Li⁺[EO]:[Li⁺]=15:1) are shown in FIG. 9A. These FAST-PEO blends exhibitedsimilar ionic conductivities as their corresponding sodium salts inliquid electrolytes: blends with Li salts A and A-PipF₄ have ionicconductivities that are 2 and 4 times lower, respectively, than that ofLiTFSI. Polymer electrolytes containing Li salts of A-PipONeop₂F₂ andA-ONeop₃F₂ showed conductivities in the range from 60° C. to 80° C. thatwere approximately one order of magnitude lower than that of LiTFSI. Asin liquid electrolyte, the lower ion conductivity of FAST-PEO blends canbe attributed to higher Lewis basicity of these salts and the formationof more ion pairs (FIG. 9B), leading to lower concentration of chargecarriers. Another reason for lower ion conductivity can simply be theirlarger size, as mobility of the FAST anions with more substitutionswould decrease and contribute less to overall ionic conductivity inthese polymer electrolytes. Nevertheless, in light of the all of theresults discussed above, A-ONeop₃F₂ shows chemical and oxidativestability on par with TFSI and reasonable conductivity, thus suggestingthe potential use of this and other tris-neopentyl substituted FASTsalts as functional TFSI replacements.

In summary, a class of sulfonimide salts for solid-state electrolytescan be synthesized based on successive S_(N)Ar reactions of fluorinatedphenyl sulfonimides: Fluorinated Aryl Sulfonimide Tags (FAST). Using DFTcalculations and experimental measurements, it was demonstrated that thechemical and electrochemical oxidative stability of these FAST salts areinversely correlated with the number of fluorine atoms present on thearomatic ring. FAST salts with strongly electron donating Pipsubstituents generally showed better chemical stability compared tothose with ether substituents; however, the sterically hindered saltA-ONeop₃F₂ was also highly resistant to chemical degradation. FAST saltswith Pip groups were more vulnerable to oxidation than those containingonly ether substituents; here again, ONeop₃F₂ displayed outstandingstability. Other properties like solubility, Lewis basicity, andconductivity can also be tuned by introducing different numbers andtypes of nucleophilic functional groups to the FAST salt scaffold. FASTsalts provide a new anion design strategy, enabling alternatives to TFSIwith properties that can be rationally designed in a highly modularfashion. In particular, the ability to readily control the pattern offunctionalization on the FAST scaffold and predict the resultingchemical and oxidative stability as well as basicity opens up newopportunities for the design of polymer-FAST conjugates and single-ionconductors, meeting the growing interest of solid-state electrolytes aspotentially safe and stable high-energy storage technologies.

Theoretical Calculations

All calculations were performed employing the Gaussian 09 computationalpackage. See M. J. Gaussian, Revision A., Frisch, G. W. Trucks, H. B.Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V.Barone, B. Mennucci and G. A. Petersson et al., 2016, which isincorporated by reference in its entirety. Geometries were optimized atthe B3LYP/6-31G(d,p) level of theory; ground states were verified by theabsence of any imaginary frequency. Natural Population Analysis (NPA)atomic partial charges were obtained using the optimized geometries atB3LYP/6-31G(d,p). See D. Becke, J. Chem. Phys., 1993, 98, 5648, Lee, W.Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785-789, A. E. Reed, R. B.Weinstock, and F. Weinhold, “Natural-population analysis,” J. Chem.Phys., 1985, 83, 735-46, and J. P. Foster and F. Weinhold, “Naturalhybrid orbitals,” J. Am. Chem. Soc., 1980, 102, 7211-18, each of whichis incorporated by reference in its entirety. Single point energycalculations were performed at the B3LYP/6-311++G(d,p) level of theoryfor oxidation energies, nucleophilic substitution free energies, andcation-anion association free energies. The conductor-like polarizablecontinuum model (CPCM) was employed to capture the solvation effects.See L. Xing, O. Borodin, D. Smith and W. Li, J. Phys. Chem. C, 2011,13896-13905, and S. T. Tti, Pure Appl. Chem., 1986, 58, 955-966, each ofwhich is incorporated by reference in its entirety. Electrochemicaloxidative stability is estimated by oxidation energy calculations, whichis the Gibbs free energy for the electrochemical oxidation reactionM→M⁺+e⁻ in the solution (Dimethyl sulfoxide (DMSO) was selected as theuniversal solvent in the electrochemical oxidation energy calculations):

G _(Ox) =G(M ⁺)−G(M)

The computed electrochemical oxidation energy, G_(Ox), in eV isconverted to the experimentally measured scale versus Li/Li⁺ by thesubtraction of 1.4 V. See M. Cossi, N. Rega, G. Scalmani and V. Barone,J. Comput. Chem., 2003, 24, 669-681, and V. Barone and M. Cossi, J.Phys. Chem. A, 1998, 102, 1995-2001, each of which is incorporated byreference in its entirety. The free energies of nucleophilicsubstitution (ΔG_(nuc)) of select carbon sites in A-OMe₃F₂, A-PipOMe₂F₂,and A-Pip₂OMeF₂ were computed by superoxide in implicit DMSO. To mimicthe solvation environment in 1,2-dimethoxyethane (DME) solvent,diethylether was selected as the implicit solvent in the associationfree energy calculation, and the dielectric constant of the implicitsolvent was set to 7.2. The likelihood of cation-anion interaction wasestimated by the Gibbs free energy of the reaction M⁺+A⁻→MA (M=Na orLi), which is taken to be the association free energy in the solution:

ΔG _(asso) =G(MA)−G(M ⁺)−G(A ⁻)

G(M⁺) is approximated according to the reaction M⁺+2DME→M⁺(DME)₂, where

G(M ⁺)=G(M ⁺(DME)₂)−2G(DME)

Electrochemical Stability Test Details

The sulfonimide compounds were vacuum-dried at 75° C. overnight beforebeing transferred into a glove box (H₂O<0.1 ppm, O₂<0.1 ppm, MBraun,USA) without exposure to the atmosphere. The oxidative stability of thesulfonimide compounds was studied in electrochemical cells consisting ofa Lithium foil (D=15 mm, Chemetall, Germany), 90 μL of 0.02 Msulfonimide sample in propylene carbonate (H₂O<20 ppm by Karl Fischertitration, BASF), one piece of glass fiber separator (D=18 mm, Whatman®,Grade GF/A), and a 304 stainless steel mesh as current collector (D=12.7mm). The assembled electrochemical cells were then transferred to asecond glove box (H₂O<1 ppm, O₂<1%, MBraun, USA) and pressured with dryO₂ (99.994% purity, H₂O<2 ppm, Airgas, USA) to 30 psi (gauge). In eachelectrochemical stability test, after holding the cell at open circuitvoltage for two hours, a series of potentials were applied sequentiallyfor three hours each: 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, and 4.5 V;the current response was recorded throughout the test. Allelectrochemical tests were conducted employing a VMP3 potentiostat(BioLogic Science Instruments).

Conductivity Measurement Details

The impedance measurements were conducted using electrochemical cellsconsisting of liquid or polymer electrolytes sandwiched between twostainless steel blocking electrodes (D=15.5 mm). The liquid electrolytecontained one piece of Celgard 2340 separator (thickness=38 m,porosity=0.45) impregnated with 100 μL of 0.1 M sulfonimide sample in1,2-dimethoxyethane (purchased from Acros, degassed and dried using aglass contour solvent purification system by SG Water USA, LLC), whereasthe polymer electrolytes contained 10 k PEO-sulfonimide blends([EO]:[Li+]=15:1). The conductivity was studied with electrochemicalimpedance spectroscopy (EIS, VMP3, Bio-Logic Science Instruments) overthe frequency range of 1 MHz and 0.1 Hz at a voltage amplitude of 10 mV.The bulk electrolyte conductivity, a, is estimated from the bulkelectrolyte resistance, R, obtained in the EIS measurement according tothe equation

$\sigma = {\frac{1}{R}\frac{d}{A}}$

where d is the thickness of the electrolyte (i.e., the thickness of theseparator for liquid electrolyte, and the thickness of thePEO-sulfonimide sample for polymer electrolyte) and A is thecross-sectional area of tested sample.

²³Na NMR Measurement of Interaction Between Anion and Cations Among FASTSalts

For A type FAST salts, nitromethane was chosen as the solvent since ithas lower value of Gutmann's donor numbers than TFSI anion. See R. H.Erlich, A. I. Popov, J. Am. Chem. Soc. 93, 5620-5623 (1971), and M.Schmeisser, P. Ilner, R. Puchta, A. Zahl, R. van Eldik, Chemistry 18,10969-10982 (2012), each of which is incorporated by reference in itsentirety. FAST salts were dissolved in nitromethane to prepare 0.1 Msolution and loaded into thin wall NMR tube. The inner reference was a0.25 M DMSO solution of sodium perchlorate. For measurements, thereference solution was placed in a capillary sealed by PTFE cap andinserted coaxially into the sample NMR tube. The ²³Na spectra werecollected at Bruker 106 MHz, and the chemical shift of the reference wasset to 0 ppm. Since B type and C type salts have low solubility innitromethane, acetonitrile was chosen as the solvent. The reference andmeasurement details were the same as in A type salts.

TABLE 1 Crystal data A11 A12 A13 S2 Empirical formula C₂₄H₂₀F₅N₂NaO₆S₂C₁₄H₁₈F₅N₂NaO₇S₂ C₁₆H₂₀F₅N₂NaO₆S₂ C₁₇H₂₁F₆N₃O₄S₂ a 43.264 Å 7.958 Å5.399 Å 8.153 Å b 5.590 Å 28.725 Å 11.412 Å 11.052 Å c 24.240 Å 8.954 Å18.037 Å 12.536 Å α (alpha): 90.00° 90.00° 82.42° 99.43° β (beta):119.48° 91.06° 82.10° 94.08° γ (gamma): 90.00° 90.00° 86.02° 110.56°Volume: 5103.33 Å³ 2046.48 Å³ 1089.67 Å³ 1033.16 Å³ Space group: C2/cP2₁/n P-1 P-1 Calculated density: 1.600 g/cm³ 1.650 g/cm³ 1.580 g/cm³1.638 g/cm³ Color: colourless colourless colourless colourless Z: 8 4 22 Temperature: −173.0° C. −173.0° C. −123.0° C. −173.0° C. Formulaweight: 614.546 g/mole 508.420 g/mole 518.458 g/mole 509.494 g/moleR(F): 0.0386 0.0741 0.0321 0.0301 R_(w)(F²): 0.0969 0.1601 0.0891 0.0836

TABLE 2 Melting points of representative salts Samples (sodium salts)T_(m) (° C.) A-PipOMe₂F₂ 264-265 A-PipOEt₂F₂ 252-253 A-PipOiPr₂F₂235-239 A-PipONeop₂F₂ 216-222 A-ONeop₃F₂ 206-214

Synthesis Part:

2,3,4,5,6-pentafluoro-N-[(trifluoromethyl)sulfonyl]benzene sulfonamide(A): To a 100 mL round-bottomed flask equipped with a magnetic stirringbar were added trifluoromethane sulfonamide (10.0 mmol),N-methylmorpholine (20.0 mmol), and 50 mL DCM. The mixture was cooled to0° C. With stirring, 2,3,4,5,6-pentafluorobenzene sulfonyl chloride(10.5 mmol) in 10 mL DCM was added dropwise via dropping funnel. Thesolution was further stirred at room temperature for 24 h. Afterremoving DCM solvent under vacuum, the residue was dissolved in 100 mLethyl acetate, and washed with 1M hydrochloric acid (1×50 mL), water(1×40 mL) and brine solution (2×40 mL). Then organic layer was driedover anhydrous sodium sulfate and concentrated in vacuum. The residuewas purified by flash chromatography on silica gel with acetone/hexanes(v/v=1/2) as the eluent to afford the product as a white solid (3.28 g,82%). ¹³C NMR (126 MHz, acetone-d⁶, ppm, δ): 139.53 (dm, J=255.7 Hz),138.33 (dm, J=257.0 Hz), 132.84 (dm, J=253.2 Hz), 115.14 (q, J=321.7Hz), 115.27-114.30 (m). ¹⁹F NMR (125 MHz, acetone-d⁶, ppm, δ): −79.33,−137.86, −152.84, −164.07. MS (m/z): Calc. for C₇NF₈O₄S₂Na: 400.9. Found(M-Na)⁻: 377.9.

A-ONeopF₄ & A-ONeop₂F₃:

To a 20 mL vial equipped with a magnetic stirring bar were added dryneopentanol (5.7 mmol), sodium hydride (5.7 mmol) and 5 mL dry DMF undernitrogen. After stirred at room temperature for 0.5 h, the mixture wastransferred dropwise to another 40 ml vial which has been charged with A(4.0 mmol) and 5 mL DMF first. The solution was quenched by adding 5 ml1M HCl aqueous solution after further stirred at room temperature for 2h. Then ethyl acetate (2×50 mL) was added to extract crude product, andwashed with water (1×30 mL) and brine solution (2×30 mL). Then organiclayer was dried over anhydrous sodium sulfate and concentrated invacuum. The residue was purified by flash chromatography on silica gelwith acetone/hexanes (v/v=1/2) as the eluent to afford the products aswhite foam solids.

A-ONeopF₄:

(0.79 g, 42%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.05 (s, 2H), 1.06(s, 9H). ¹³C NMR (126 MHz, acetone-d₆, ppm) δ:145.44 (dm, J=253.3 Hz),140.61 (dm, J=245.0 Hz), 141.03-140.32 (m), 120.19 (q, J=320.0 Hz),118.61-117.32 (m), 84.72, 32.40, 25.31. ¹⁹F NMR (376 MHz, acetone-d₆,ppm) δ: −79.23, −139.80, −159.45. MS (m/z): Calc. for C₁₂H₁₁NF₇O₅S₂Na:468.99. Found (M-Na)⁻: 446.0.

A-ONeop₂F₃:

(0.77 g, 36%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 3.95 (s, 2H), 3.84(s, 2H), 1.04 (s, 9H), 1.03 (s, 9H). ¹³C NMR (126 MHz, acetone-d₆, ppm)δ: 146.06 (dm, J=246.9 Hz), 144.65 (dm, J=252.0 Hz), 142.35 (m), 140.37(dm, J=245.7 Hz), 140.70-140.05 (m), 120.28 (q, J=322.6 Hz),123.46-122.40 (m), 84.55, 84.13, 32.40, 32.12, 26.06, 25.45. ¹⁹F NMR(376 MHz, acetone-d₆, ppm) δ: −78.78, −139.45, −150.64, −160.30. MS(m/z): Calc. for C₁₇H₂₂NF₆O₆S₂Na: 537.07. Found (M-Na)⁻ 514.1.

General Procedure for A-OR₃F₂:

A 40 mL vial equipped with a magnetic stirring bar was charged with A(1.2 mmol) and 5 mL dry DMF. Then corresponding sodium phenoxide oralkoxide (6.0 mmol) was added under nitrogen. After stirred at roomtemperature (90° C. for sodium phenoxide) for 12 h, the solution wasquenched by adding 10 ml 1M HCl aqueous solution. Then ethyl acetate(2×30 mL) was added to extract crude product, and washed with water(1×20 mL) and brine solution (2×20 mL). The organic layer was dried overanhydrous sodium sulfate and concentrated in vacuum. The residue waspurified by flash chromatography on silica gel with acetone/hexanes(v/v=1/2) as the eluent to afford the products as white solids.

A-OPh₃F₂:

(0.62 g, 83%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 7.45-7.30 (m, 4H),7.17-7.02 (m, 6H). ¹³C NMR (101 MHz, acetone-d₆, ppm) δ: 158.50, 157.14,146.88 (dd, J=252.9, 3.4 Hz), 138.48 (dd, J=11.6, 4.3 Hz), 135.68 (t,J=13.0 Hz), 131.25, 130.10, 129.40, 123.88, 122.64, 120.77 (q, J=304.0Hz), 115.90, 115.26. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ: −77.26,−142.07. MS (m/z): Calc. for C₂₅H₁₅NF₅O₇S₂Na: 623.01. Found (M-Na)⁻:599.9.

A-OMe₃F₂:

(0.29 g, 55%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.02 (s, 3H), 3.80(s, 6H). ¹³C NMR (101 MHz, acetone-d₆, ppm) δ: 145.90 (dd, J=244.3, 4.7Hz), 143.02 (dd, J=11.5, 4.2 Hz), 139.92 (t, J=12.9 Hz), 128.17, 120.47(q, J=324.9 Hz), 62.62, 62.30. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ:−79.02, −151.70. MS (m/z): Calc. for C₁₀H₉NF₅O₇S₂Na: 437.28. Found(M-Na)⁻: 414.2.

A-OEt₃F₂:

(0.40 g, 70%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.29 (q, J=8.0 Hz,2H), 4.17 (t, J=8.0 Hz, 4H), 1.40-1.30 (t, 9H). ¹³C NMR (101 MHz,acetone-d₆, ppm) δ: 146.34 (dd, J=244.5, 4.6 Hz), 142.00 (dd, J=11.8,4.3 Hz), 139.23 (t, J=13.6 Hz), 127.55, 120.24 (q, J=322.7 Hz), 71.59,70.47, 14.87, 14.67. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ: −78.93,−150.74. MS (m/z): Calc. for C₁₃H₁₅NF₅O₇S₂Na: 479.36. Found (M-Na)⁻:456.0.

A-OiPr₃F₂:

(0.49 g, 78%). ¹H NMR (400 MHz, DMSO-d₆, ppm) δ: 4.67-4.55 (m, 2H),4.53-4.40 (m, 1H), 1.28 (d, J=8.0 Hz, 6H), 1.21 (d, J=8.0 Hz, 12H). ¹³CNMR (101 MHz, acetone-d₆, ppm) δ: 146.73 (dd, J=242.5, 4.5 Hz), 140.77(dd, J=11.8, 4.1 Hz), 137.70 (t, J=14.3 Hz), 128.93, 120.37 (q, J=323.2Hz), 78.19-77.31 (m), 77.44, 21.72, 21.41. ¹⁹F NMR (376 MHz, DMSO-d₆,ppm) δ: −77.31, −146.44. MS (m/z): Calc. for C₁₆H₂₁NF₅O₇S₂Na: 521.06.Found (M-Na)⁻: 497.9.

A-ONeop₃F₂:

(0.54 g, 75%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 3.88 (s, 2H), 3.82(s, 4H), 1.05 (s, 9H), 1.04 (s, 18H). ¹³C NMR (101 MHz, acetone-d₆, ppm)δ: 146.07 (dd, J=244.2, 4.6 Hz), 142.61 (dd, J=11.0, 4.2 Hz), 140.04 (t,J=13.3 Hz), 128.39, 120.47 (q, J=323.6 Hz), 84.33, 84.16, 32.39, 32.13,26.16, 25.55. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ: −78.19, −145.87. MS(m/z): Calc. for C₂₂H₃₃NF₅O₇S₂Na: 605.15. Found (M-Na)⁻: 582.1.

A-PipF₄:

To a 50 mL round-bottomed flask equipped with a magnetic stirring barwere added A (5.0 mmol), piperidine (7.5 mmol), triethylamine (10.0mmol), and 20 mL acetonitrile. The mixture was further stirred at roomtemperature for 12 h. After removing acetonitrile under vacuum, theresidue was dissolved in 30 mL ethyl acetate, and washed with 1Mhydrochloric acid (1×20 mL), water (1×20 mL) and brine solution (2×20mL). Then organic layer was dried over anhydrous sodium sulfate andconcentrated in vacuum. The residue was purified by flash chromatographyon silica gel with acetone/hexanes (v/v=1/2) as the eluent to afford theproduct as a pale yellow solid (1.86 g, 80%). ¹H NMR (400 MHz,acetone-d₆, ppm) δ: 3.33-3.27 (m, 4H), 1.75-1.60 (m, 6H). ¹³C NMR (101MHz, acetone-d₆, ppm) δ: 144.54 (dm, J=253.5 Hz), 141.24 (dm, J=243.4Hz), 133.53 (m), 120.25 (q, J=323.9 Hz), 115.76 (m), 51.81, 26.27,23.74. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ: −77.96, −140.13, −151.99.MS (m/z): Calc. for C₁₂H₁₀N₂F₇O₄S₂Na: 466.0. Found (M-Na)⁻: 443.0.

A-PipOiPrF₃:

To a 40 mL vial equipped with a magnetic stirring bar were added A-PipF₄(1.0 mmol) and 5 mL DMF. Sodium isopropoxide (1.0 mmol) was then addedunder nitrogen and stirred at room temperature for 2 h. The reaction wasquenched by adding 2 mL 1M hydrochloric acid, and diluted with 30 mLethyl acetate. The organic layer was washed with water (1×20 mL) andbrine solution (2×20 mL), dried over anhydrous sodium sulfate andconcentrated in vacuum. The residue was purified by flash chromatographyon silica gel with acetone/hexanes (v/v=1/2) as the eluent to afford theproduct as pale yellow solid (0.26 g, 52%). H NMR (400 MHz, acetone-d₆,ppm) δ: 4.75-4.63 (m, 1H), 3.32-3.20 (m, 4H), 1.72-1.57 (m, 6H), 7.56(dd, J=6.2, 1.2 Hz, 6H). ¹³C NMR (101 MHz, acetone-d₆, ppm) δ: 147.22(dm, J=243.41), 145.29 (dm, J=251.49 Hz), 142.67 (dd, J=16.5, 6.5 Hz),141.07-139.28 (m), 133.80-132.50 (m), 121.57 (d, J=11.4 Hz), 120.35 (q,J=281.8 Hz), 77.97, 51.94, 26.36, 23.86, 21.47. ¹⁹F NMR (376 MHz,acetone-d₆, ppm) δ: −78.94, −138.46, −141.21, −153.83. MS (m/z): Calc.for C₁₅H₁₇N₂F₆O₅S₂Na: 506.0. Found (M-Na)⁻: 482.9.

General Procedure for A-PipOR₂F₂:

A 40 mL vial equipped with a magnetic stirring bar was charged withA-PipF₄ (1.2 mmol) and 5 mL dry DMF. Then corresponding sodium phenoxideor alkoxide (4.0 mmol) was added under nitrogen. After stirred at roomtemperature (90° C. for sodium phenoxide) for 12 h, the solution wasquenched by adding 10 ml 1M HCl aqueous solution. Then ethyl acetate(2×30 mL) was added to extract crude product, and washed with water(1×20 mL) and brine solution (2×20 mL). The organic layer was dried overanhydrous sodium sulfate and concentrated in vacuum. The residue waspurified by flash chromatography on silica gel with acetone/hexanes(v/v=1/2) as the eluent to afford the products as white solids.

A-PipOPh₂F₂

(0.63 g, 85%). ¹H NMR (400 MHz, DMSO-d₆, ppm) δ: 7.35-7.25 (m, 4H),7.07-7.00 (m, 2H), 6.95-6.87 (m, 4H), 3.15-3.08 (m, 4H), 1.58-1.50 (m,6H). ¹³C NMR (101 MHz, acetone-d₆, ppm) δ: 158.78, 147.40 (dd, J=247.9,6.7 Hz), 137.79 (dd, J=12.1, 5.7 Hz), 133.71 (t, J=11.7 Hz), 129.15,126.59, 122.04, 120.51 (q, J=317.2 Hz), 115.80, 51.93, 26.31, 23.80. ¹⁹FNMR (376 MHz, DMSO-d₆, ppm) δ: −77.24, −137.96. MS (m/z): Calc. forC₂₄H₂₀N₂F₅O₆S₂Na: 614.06. Found (M-Na)⁻: 591.1.

¹³C NMR (101 MHz, Acetone-d₆) δ.

A-PipOMe₂F₂

(0.40 g, 68%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 3.90 (s, 8H),3.26-3.20 (m, 4H), 1.73-1.57 (m, 6H). ¹³C NMR (100 MHz, acetone-d₆, ppm)δ: 147.33 (dd, J=250.0, 4.0 Hz), 144.52 (dd, J=13.1, 4.0 Hz), 134.52 (t,J=11.2 Hz), 129.04, 121.24 (q, J=324.5 Hz), 63.44, 57.20, 24.75, 22.17.¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ: −79.56, −144.30. MS (m/z): Calc.for C₁₄H₁₆N₂F₅O₆S₂Na: 490.03. Found (M-Na)⁻: 466.9.

A-PipOEt₂F₂

(0.46 g, 74%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.02 (q, J=8.0 Hz,4H), 3.11-3.03 (m, 4H), 1.58-1.40 (m, 6H), 1.22 (t, J=8.0 Hz, 6H). ¹³CNMR (101 MHz, acetone-d₆, ppm) δ: 147.50 (dd, J=242.9, 6.6 Hz), 141.99(dd, J=12.6, 4.8 Hz), 133.18 (t, J=12.3 Hz), 126.10, 120.33 (q, J=323.0Hz), 71.20, 52.04, 26.44, 23.95, 14.76. ¹⁹F NMR (376 MHz, acetone-d₆,ppm) δ: −78.70, −143.91. MS (m/z): Calc. for C₁₆H₂₀N₂F₅O₆S₂Na: 518.06.Found (M-Na)⁻: 495.0.

A-PipOiPr₂F₂:

(0.47 g, 72%). ¹H NMR (400 MHz, DMSO-d₆, ppm) δ: 4.62-4.50 (m, 2H),3.15-3.07 (m, 4H), 1.65-1.50 (m, 6H), 1.20 (d, J=8.0 Hz, 12H). ¹³C NMR(101 MHz, acetone-d₆, ppm) δ: 147.36 (dd, J=241.6, 6.6 Hz), 140.67 (dd,J=12.4, 4.7 Hz), 132.67 (t, J=12.8 Hz), 127.10, 120.36 (q, J=323.1 Hz),77.48, 52.08, 26.46, 23.97, 21.45. ¹⁹F NMR (376 MHz, DMSO-d₆, ppm) δ:−77.55, −140.70. MS (m/z): Calc. for C₁₈H₂₄N₂F₅O₆S₂Na: 546.09. Found(M-Na)⁻: 522.9.

A-PipONeop₂F₂:

(0.59 g, 81%). ¹H NMR (400 MHz, acetonitrile-d₃, ppm) δ: 3.77 (s, 4H),3.24-3.17 (m, 4H), 1.72-1.57 (m, 6H), 1.05 (s, 18H). ¹³C NMR (101 MHz,acetone-d₆, ppm) δ: 147.64 (dd, J=243.1, 6.5 Hz), 142.43 (dd, J=12.0,4.6 Hz), 133.08 (t, J=12.3 Hz), 127.22, 120.50 (q, J=323.7 Hz), 83.94,52.10, 32.10, 26.47, 26.19, 23.99. ¹⁹F NMR (376 MHz, acetonitrile-d₃,ppm) δ: −78.70, −143.30. (LC-MS, m/z): Calc. for C₂₂H₃₂N₂F₅O₆S₂Na:602.15. Found (M-Na)⁻: 579.0.

A-PipOEtOiPrF₂:

A 40 mL vial equipped with a magnetic stirring bar was charged withA-PipOiPrF₃ (0.5 mmol) and 4 mL dry DMF. Then sodium ethoxide (1.5 mmol)was added under nitrogen and stirred at room temperature for 12 h. Thereaction was quenched by adding 5 ml 1M HCl aqueous solution. Then ethylacetate (30 mL) was added to extract crude product, and washed withwater (1×20 mL) and brine solution (2×20 mL). The organic layer wasdried over anhydrous sodium sulfate and concentrated in vacuum. Theresidue was purified by flash chromatography on silica gel withacetone/hexanes (v/v=1/2) as the eluent to afford the product as whitesolids (0.20 g, 77%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.75-4.57 (m,1H), 4.18 (q, J=7.0 Hz, 2H), 3.25-3.15 (m, 4H), 1.72-1.57 (m, 6H), 1.38(t, J=7.0 Hz, 3H), 1.28 (d, J=6.1 Hz, 6H). ¹³C NMR (101 MHz, acetone-d₆,ppm) δ: 148.73 (dd, J=12.9, 6.6 Hz), 146.32 (dd, J=13.9, 6.6 Hz), 142.48(dd, J=13.4, 3.8 Hz), 140.29 (dd, J=13.7, 3.6 Hz), 132.85 (t, J=12.6Hz), 126.91, 120.41 (q, J=323.2 Hz), 77.86, 70.86, 52.06, 26.45, 23.96,21.43, 14.76. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ: −77.26, −140.26,−142.90. MS (m/z): Calc. for C₁₇H₂₂N₂F₅O₆S₂Na: 532.07. Found (M-Na)⁻:509.1.

A-o-PipONeop₂F₂:

was synthesized by two more steps:

A 40 mL vial equipped with a magnetic stirring bar was charged withA-ONeopF₄ (0.7 mmol), piperidine (2.0 mmol) and 5 mL acetonitrile. Themixture was stirred at 60° C. for 12 h under nitrogen. Then 20 mL 1M HClwas added to the reaction. The white precipitate was filtered, washedwith saturate sodium carbonate solution (20 mL), water (2×30 mL), anddried in vacuum to afford the product A-o-PipONeopF₃ as white solids(0.20 g, 77%). ¹H NMR (500 MHz, DMSO-d₆, ppm) δ: 3.89 (s, 1H), 3.05-2.85(m, 4H), 1.94-1.13 (m, 6H), 0.98 (s, 9H). ¹³C NMR (100 MHz, DMSO-d₆,ppm) δ: 151.95 (d, J=248.7 Hz), 144.97 (dd, J=253.0, 11.3 Hz), 141.95(ddd, J=246.9, 17.6, 5.1 Hz), 139.63 (t, J=11.3 Hz), 135.92 (d, J=13.1Hz), 127.48 (d, J=6.6 Hz), 120.46 (q, J=324.9 Hz), 84.53, 52.00, 32.76,26.08, 25.80, 24.20. ¹⁹F NMR (376 MHz, DMSO-d₆, ppm) δ: −77.33, −137.57,−140.21, −155.25. MS (m/z): Calc. for C₁₇H₂₁N₂F₆O₅S₂Na: 534.07. Found(M-Na)⁻: 511.1.

To a 20 mL vial equipped with a magnetic stirring bar were added dryneopentanol (1.0 mmol), sodium hydride (1.0 mmol) and 3 mL dry DMF undernitrogen. After stirred at room temperature for 0.5 h, the mixture wastransferred dropwise to another 40 ml vial which has been charged withA-o-PipONeopF₃ (0.4 mmol) and 3 mL DMF first. The reaction was quenchedby adding 20 ml 1M HCl aqueous solution after further stirred at roomtemperature for 4 h. The white precipitate was filtered and washed bywater (3×20 mL). The collected solids were dissolved in 30 mL ethylacetate, washed with 1M NaOH (1×15 mL), water (1×20 mL) and brinesolution (2×20 mL). The organic layer was dried over anhydrous sodiumsulfate, concentrated and dried in vacuum to afford the productA-o-PipONeop₂F₂ as white solids (0.20 g, 85%). %). ¹H NMR (400 MHz,DMSO-d₆, ppm) δ: 3.72 (s, 2H), 3.67 (s, 2H), 3.05-2.80 (m, 4H),2.80-2.60 (m, 4H), 2.00-1.50 (m, 6H), 1.40-1.00 (m, 6H), 0.91 (d, J=8.7Hz, 18H). ¹³C NMR (100 MHz, acetone-d₆, ppm) δ: 151.43 (dd, J=477.7, 6.1Hz), 148.98 (dd, J=475.7, 6.1 Hz), 143.05 (dd, J=11.2, 4.1 Hz), 139.55(t, J=13.8 Hz), 136.12 (dd, J=12.6, 4.1 Hz), 133.04 (d, J=3.4 Hz),120.66 (q, J=324.7 Hz), 84.20, 51.71, 35.97, 32.37, 32.06, 26.18, 25.66,25.54, 24.24. ¹⁹F NMR (376 MHz, DMSO-d₆, ppm) δ: −77.92, −141.28,−147.45. MS (m/z): Calc. for C₂₂H₃₂N₂F₅O₆S₂Na: 602.15. Found (M-Na)⁻:579.1.

A-Pip₂F₃.H⁺:

To a 50 mL round-bottomed flask equipped with a magnetic stirring barwere added A (3.0 mmol), piperidine (10 mmol), triethylamine (10.0mmol), and 20 mL acetonitrile. The mixture was further stirred at 70° C.for 12 h. After removing acetonitrile under vacuum, the residue wasdissolved in 30 mL ethyl acetate, and washed with 1M hydrochloric acid(1×20 mL), water (1×20 mL) and brine solution (2×20 mL). Then organiclayer was dried over anhydrous sodium sulfate and concentrated invacuum. The residue was purified by flash chromatography on silica gelwith acetone/hexanes (v/v=1/2) as the eluent to afford the product aswhite solid (1.86 g, 65%), which is the protonated state of A-Pip₂F₃. ¹HNMR (400 MHz, CDCl₃, ppm) δ: 11.69 (s, 1H), 3.90-3.65 (m, 4H), 3.35-3.25(m, 4H), 2.15-1.95 (m, 5H), 1.75-1.65 (m, 6H), 1.65-1.55 (m, 1H). ¹³CNMR (101 MHz, CDCl₃, ppm) δ: 153.62 (dd, J=244.8, 5.1 Hz), 144.78 (dd,J=250.8, 13.5 Hz), 143.16 (dm, J=245.4 Hz), 135.82 (d, J=15.1 Hz),133.13 (t, J=11.0 Hz), 125.16, 120.29 (q, J=322.9 Hz), 51.96, 51.75,26.38, 25.72, 24.18, 23.88 ¹⁹F NMR (376 MHz, CDCl3, ppm) δ: −78.42,−129.52, −132.39, −138.54. MS (m/z): Calc. for C₁₇H₂₁N₃F₆O₄S₂: 466.07.Found (M-H)⁻: 508.1.

A-Pip₂F₃:

A-Pip₂F₃.H⁺ was dissolved in 30 mL ethyl acetate, washed with 1M NaOH(1×15 mL), water (1×20 mL) and brine solution (2×20 mL). The organiclayer was dried over anhydrous sodium sulfate, concentrated and dried invacuum to afford the products as white solids. ¹H NMR (400 MHz,acetone-d₆, ppm) δ: 3.26-3.16 (m, 4H), 3.10-2.92 (m, 4H), 1.95-1.77 (m,2H), 1.75-1.65 (m, 7H), 1.52-1.40 (m, 2H), 1.37-1.20 (m, 1H). ¹³C NMR(100 MHz, acetone-d₆, ppm) δ: 151.75 (dd, J=258.6, 15.1 Hz), 150.12 (dm,J=250.5 Hz), 149.36 (dm, J=255.5 Hz), 139.60-139.22 (m), 126.27-125.09(m), 123.48 (q, J=323.2 Hz), 120.02 (d, J=16.7 Hz), 60.30 (d, J=6.3 Hz),56.00, 30.18, 28.64, 27.62, 24.95. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ:−79.23, −133.23, −141.02, −150.07. MS (m/z): Calc. for C₁₇H₂₀N₃F₆O₄S₂Na:531.07. Found (M-H)⁻: 508.1.

General Procedure for A-Pip₂ORF₂:

A 40 mL vial equipped with a magnetic stirring bar was charged withA-Pip₂F₃.H⁺ (0.7 mmol) and 4 mL dry DMF. Then corresponding sodiumalkoxide (2.0 mmol) was added under nitrogen and the mixture was stirredat room temperature for 4 h. The reaction was quenched by adding 20 ml1M HCl aqueous solution. The white precipitate was filtered and washedby water (3×20 mL). The collected solids were dissolved in 30 mL ethylacetate, washed with 1M NaOH (1×15 mL), water (1×20 mL) and brinesolution (2×20 mL). The organic layer was dried over anhydrous sodiumsulfate, concentrated and dried in vacuum to afford the products aswhite solids.

A-Pip₂OMeF₂

(0.31 g, 81%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 3.89 (s, 3H),3.25-3.18 (m, 4H), 3.14-2.95 (m, 4H), 2.00-1.85 (m, 2H), 1.75-1.57 (m,7H), 1.50-1.40 (m, 2H), 1.37-1.23 (m, 1H). ¹³C NMR (126 MHz, acetone-d₆,ppm) δ: 151.81 (dd, J=716.6, 7.0 Hz), 150.83 (dd, J=718.4, 7.0 Hz),142.57 (dd, J=14.7, 3.8 Hz), 136.09 (dd, J=14.7, 3.8 Hz), 133.43-132.41(m), 130.88 (d, J=4.4 Hz), 120.30 (q, J=322.9 Hz), 62.83, 52.07, 51.70,26.48, 25.70, 24.26, 23.99. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ:−79.38, −132.55, −141.28. MS (m/z): Calc. for C₁₈H₂₃N₃F₅O₅S₂Na: 543.09.Found (M-Na)⁻: 520.1.

A-Pip₂OEtF₂

(0.30 g, 78%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.12 (q, J=8.0 Hz,2H), 3.23-3.15 (m, 4H), 3.14-2.94 (m, 4H), 2.04-1.87 (m, 2H), 1.75-1.57(m, 7H), 1.50-1.37 (m, 2H), 1.37-1.23 (m, 1H), 1.33 (t, J=8.0 Hz, 3H).¹³C NMR (101 MHz, CDCl₃, ppm) δ: 151.81 (dd, J=254.4, 7.1 Hz), 147.43(d, J=7.1 Hz), 145.20-144.75 (m), 134.93 (t, J=12.1 Hz), 122.51 (d,J=4.1 Hz), 122.35, 119.70 (q, J=323.2 Hz), 72.20, 55.85, 52.21, 26.40,24.75, 23.90, 21.33, 15.42. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ:−78.78, −133.32, −140.70. MS (m/z): Calc. for C₁₉H₂₅N₃F₅O₅S₂Na: 557.11.Found (M-Na)⁻: 534.1.

A-Pip₂OiPrF₂

(0.31 g, 78%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.52-4.40 (m, 1H),3.24-3.14 (m, 4H), 3.14-2.95 (m, 4H), 2.00-1.85 (m, 2H), 1.75-1.55 (m,7H), 1.50-1.40 (m, 2H), 1.37-1.23 (m, 1H), 1.28 (d, J=8.0 Hz, 6H). ¹³CNMR (126 MHz, acetone-d₆, ppm) δ: 152.85 (dd, J=671.6, 6.3 Hz), 150.92(dd, J=662.1, 6.3 Hz), 140.02 (dd, J=13.0, 6.3 Hz), 136.06 (dd, J=14.0,6.3 Hz), 132.58 (t, J=12.5 Hz), 132.04, 120.33 (q, J=323.8 Hz), 78.67,51.97, 51.56, 26.36, 25.51, 24.12, 23.87, 21.19. ¹⁹F NMR (376 MHz,DMSO-d₆, ppm) δ: −79.11, −132.63, −137.55. MS (m/z): Calc. forC₂₀H₂₇N₃F₅O₅S₂Na: 571.12. Found (M-Na)⁻: 548.1.

A-Pip₂ONeopF₂

(0.32 g, 77%). ¹H NMR (400 MHz, acetonitrile-d₃, ppm) δ: 3.77 (s, 2H),3.28-3.14 (m, 4H), 3.14-2.95 (m, 4H), 2.05-1.87 (m, 2H), 1.80-1.57 (m,7H), 1.52-1.40 (m, 2H), 1.37-1.23 (m, 1H), 1.04 (s, 9H). ¹³C NMR (126MHz, acetonitrile-d₃, ppm) δ: 152.93 (dd, J=632.5, 6.1 Hz), 150.98 (dd,J=630.0, 6.1 Hz), 142.87 (dd, J=13.0, 4.1 Hz), 135.94 (dd, J=14.0, 4.3Hz), 132.90-132.45 (m), 131.94 (d, J=5.0 Hz), 120.69 (q, J=324.7 Hz),84.23, 52.13, 51.60, 32.10, 26.50, 26.19, 25.74, 24.32, 24.03. ¹⁹F NMR(376 MHz, acetonitrile-d₃, ppm) δ: −78.31, −133.65, −140.51. (m/z):Calc. for C₂₂H₃₁N₃F₅O₅S₂Na: 599.15. Found (M-Na)⁻: 576.1.

B:

To a 100 mL round-bottomed flask equipped with a magnetic stirring barwere added trifluoromethane sulfonamide (8.0 mmol), N-methylmorpholine(16.0 mmol), and 40 mL DCM. The mixture was cooled to 0° C. Withstirring, 4-trifluoromethyl-2,3,5,6-tetrafluorobenzenesulfonyl bromide¹²(8.2 mmol) in 10 mL DCM was added dropwise via dropping funnel. Thesolution was further stirred at room temperature for 24 h. Afterremoving DCM solvent under vacuum, the residue was dissolved in 100 mLethyl acetate, and washed with 1M hydrochloric acid (1×30 mL), water(1×40 mL) and brine solution (2×40 mL). Then organic layer was driedover anhydrous sodium sulfate and concentrated in vacuum. The residuewas purified by flash chromatography on silica gel with acetone/hexanes(v/v=1/2) as the eluent to afford the product as a white solid (2.60 g,72%). ¹³C NMR (126 MHz, acetone-d⁶, ppm, δ): 142.10-139.55 (m), 138.16(t, J=20.3 Hz), 122.65 (t, J=15.0 Hz), 115.71 (q, J=275.2 Hz), 114.92(q, J=321.3 Hz), 108.56-103.96 (m). ¹⁹F NMR (376 MHz, acetone-d⁶, ppm,δ): −57.61, −79.58, −137.16, −141.80. MS (m/z): Calc. for C₈NF₁₀O₄S₂Na:450.90. Found (M-Na)⁻: 427.9.

The synthesis procedure of B—OR₄ was similar with A-OR₃F₂. The productwas acquired as white solids by flash chromatography on silica gel withacetone/hexanes (v/v=1/2) as the eluent.

B-OEt₄

(58%). ¹H NMR (400 MHz, acetone-d₆, ppm) δ: 4.19 (q, J=7.0 Hz, 4H), 4.09(t, J=7.0 Hz, 4H), 1.46-1.32 (m, 12H). ¹³C NMR (101 MHz, acetone-d₆,ppm) δ: 148.03, 147.64, 137.53, 123.18 (q, J=276.1 Hz), 120.80 (q,J=28.2 Hz), 120.33 (q, J=323.8 Hz), 70.21, 69.99, 14.85. ¹⁹F NMR (376MHz, acetone-d₆, ppm) δ: −56.49, −78.67. (m/z): Calc. forC₁₆H₂₀NF₆O₈S₂Na: 555.04. Found (M-Na)⁻: 532.0.

B-OiPr₄

(64%). ¹H NMR (400 MHz, DMSO-d₆, ppm) δ: 4.95-4.70 (m, 4H), 1.45-1.1 (m,24H). ¹³C NMR (101 MHz, acetone-d₆, ppm) δ: 145.94, 145.44, 138.11,123.35 (q, J=276.1 Hz), 121.20 (q, J=27.2 Hz), 120.37 (q, J=324.2 Hz),76.02, 74.11, 21.33, 21.29. ¹⁹F NMR (376 MHz, DMSO-d₆, ppm) δ: −53.74,−78.89. MS (m/z): Calc. for C₂₀H₂₈NF₆O₈S₂Na: 611.11. Found (M-Na)⁻:588.1.

C:

To a 100 mL round-bottomed flask equipped with a magnetic stirring barwere added 2,3,4,5,6-pentafluorobenzene sulfonamide (10.0 mmol),N-methylmorpholine (20.0 mmol), and 60 mL DCM. The mixture was cooled to0° C. With stirring, 2,3,4,5,6-pentafluorobenzene sulfonyl chloride(10.5 mmol) in 15 mL DCM was added dropwise via dropping funnel. Thesolution was further stirred at room temperature for 24 h. Afterremoving DCM solvent under vacuum, the residue was dissolved in 100 mLethyl acetate, and washed with 1M HCl (1×30 mL), and brine solution(2×40 mL). Then organic layer was dried over anhydrous sodium sulfateand concentrated in vacuum. The residue was purified by flashchromatography on silica gel with acetone/hexanes (v/v=2/3) as theeluent to afford the product as a white solid (2.60 g, 84%). ¹³C NMR(101 MHz, acetone-d⁶, ppm, δ): 144.39 (ddd, J=255.2, 11.7, 5.8 Hz),142.43 (dm, J=255.4 Hz), 137.38 (dm, J=250.1 Hz), 120.88 (t, J=15.4 Hz).¹⁹F NMR (376 MHz, acetone-d⁶, ppm, δ): −137.72, −150.75, −162.13. MS(m/z): Calc. for C₁₂NF₁₀O₄S₂Na: 498.90. Found (M-Na)⁻: 475.9.

C-PipF₄

(75%): The synthesis procedure was similar with A-PipF₄. ¹H NMR (400MHz, DMSO-d₆, ppm) δ: 3.25-3.17 (m, 8H), 1.68-1.54 (m, 12H). ¹³C NMR(101 MHz, acetone-d₆, ppm) δ: 144.43 (dm, J=259.1 Hz), 140.99 (dm,J=240.9 Hz), 133.21, 114.80-114.0 (m), 51.86, 26.28, 23.75. ¹⁹F NMR (376MHz, DMSO-d₆, ppm) δ: −77.96, −140.13, −151.99. MS (m/z): Calc. forC₁₂H₁₀N₂F₇O₄S₂Na: 466.0. Found (M-Na)⁻: 443.0.

C-PipOEt₂F₂

(72%): The synthesis procedure was similar with A-PipOEt₂F₂. ¹H NMR (400MHz, CDCl₃, ppm) δ: 4.07 (q, J=6.8 Hz, 1H), 3.23-3.10 (m, 8H), 1.72-1.54(m, 12H), 1.36 (t, J=6.9 Hz, 12H). ¹³C NMR (101 MHz, acetone-d₆, ppm) δ:146.91 (dm, J=242.4 Hz), 142.86-142.25 (m), 135.80-134.60 (m), 117.90,71.70, 52.07, 26.53, 24.05, 14.90. ¹⁹F NMR (376 MHz, acetone-d₆, ppm) δ:−142.00. MS (m/z): Calc. for C₃₀H₄₀N₃F₄O₈S₂Na: 733.21. Found (M-Na)⁻:710.2.

C-PipOiPr₂F₂

(68%): The synthesis procedure was similar with A-PipOiPr₂F₂. ¹H NMR(400 MHz, CDCl₃, ppm) δ: 4.46-4.32 (m, 4H), 3.15-3.07 (m, 8H), 1.65-1.46(m, 12H), 1.20 (d, J=6.1 Hz, 24H). ¹³C NMR (101 MHz, CDCl₃, ppm) δ:147.23 (dd, J=242.7, 6.2 Hz), 141.68-138.40 (m), 132.82 (t, J=12.7 Hz),124.77, 78.19, 52.15, 26.60, 24.32, 22.07. ¹⁹F NMR (376 MHz, CDCl₃, ppm)δ: −139.86. MS (m/z): Calc. for C₃₄H₄₈N₃F₄O₈S₂Na: 789.27. Found (M-Na)⁻:766.2.

General Procedure for Chemical Stability Test

A 10 mL microwave vial was charged with 0.040 mmol sulfonamide salts anda stir bar, and transferred into the glove box. Then 0.5 mmol Li₂O₂, 0.5mmol KG₂, 0.040 mmol 4-Methoxybiphenyl and 0.8 mL DMF were added intothe vial. 4-Methoxybiphenyl has been proved to be stable under testcondition (see Feng, S.; Chen, M.; Giordano, L.; Huang, M.; Zhang, W.;Amanchukwu, C. V.; Anandakathir, R.; Shao-Horn, Y.; Johnson, J. A. J.Mater. Chem. A 2017, 5, 23987-23998, which is incorporated by referencein its entirety) and is chosen as the inner stand for quantitativelycalculation of survived sulfonamide salts via ¹H-NMR integration. Afterthe vial was sealed, it was moved out of the glove box and heated in anoil bath at 80° C. for 3 days. Then, the reaction mixture was cooleddown and treated with d⁶-DMSO. The mixture was further centrifuged. Theliquid layer was analyzed with ¹H, ¹⁹F-NMR, and LC-MS.

NMR results of chemical stability test are shown in FIGS. 14-44.

Other embodiments are within the scope of the following claims.

1. A composition comprising:

wherein R₁ is —CF₃ or a fluorinated phenyl and R₂ is a fluorinatedphenyl and R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by anucleophile.
 2. The composition of claim 1, wherein R₁ is —CF₃.
 3. Thecomposition of claim 1, wherein R₁ is a fluorinated phenyl.
 4. Thecomposition of claim 3, wherein the fluorinated phenyl has at least twofluorine groups. 5.-10. (canceled)
 11. The composition of claim 1,wherein the compound has formula (I) or formula (II)P-Pip_(x)OR_(y)F_(z)  (I)P-Pip_(x)OPh_(w)F_(z)  (II) wherein P is a perfluoroarylsulfonimideanion, Pip is a piperidine, OR is an alkoxide, F is a fluorinesubstituent, OPh is phenoxide, and each of x, y, z and w, independently,is 0, 1, 2 or 3, wherein the sum of x, y, and z or x, z and w is 0, 1, 2or
 3. 12.-24. (canceled)
 25. A method of making a sulfonamide comprisingcombining a sulfonamide and a sulfonyl chloride according to equation(1)

to form a first sulfonamide, wherein R₁ is —CF₃ or a fluorinated phenyland R₂ is a fluorinated phenyl.
 26. The method of claim 25, wherein R₁is —CF₃.
 27. The method of claim 25, wherein R₁ is a fluorinated phenyl.28. The method of claim 27, wherein the fluorinated phenyl has at leasttwo fluorine groups.
 29. The method of claim 25, wherein the fluorinatedphenyl has a formula

wherein each of X₁, X₂, X₃, X₄, and X₅, independently, is F or CF₃. 30.The method of claim 25, wherein the fluorinated phenyl has a formula


31. The method of claim 25, further comprising exposing the firstsulfonamide to a nucleophile according to equation (2)

wherein R₃ is —CF₃ or a fluorinated phenyl and R₄ is a fluorinatedphenyl, wherein at least one of R₃ and R₄ is substituted by thenucleophile. 32.-34. (canceled)
 35. The method of claim 25, furthercomprising: preparing a perfluoro aryl sulfonamide salt; modifying theperfluoro aryl sulfonamide salt via one or more of oxygen- and/ornitrogen-base nucleophilic aromatic substitution (S_(N)Ar) reactions tomake a composition of formula (I) or formula (II):P-Pip_(x)OR_(y)F_(z)  (I)P-Pip_(x)OPh_(w)F_(z)  (II) wherein P is a perfluoroarylsulfonimideanion, Pip is a piperidine, R is an alkoxide, F is a fluorinesubstituent, Ph is phenoxide, and each of x, y, z and w, independently,is 0, 1, 2 or 3, wherein the sum of x, y, and z or x, z and w is 0, 1, 2or 3; and making an electrolyte including the composition of theformula.
 36. The method of claim 35, wherein OR is methoxy, ethoxy,isopropoxy or neopentoxy.
 37. The method of claim 35, wherein theperfluoroarylsulfonimide salt is pentafluorobenzene sulfonyl chloride.